Detectable markers in cationic polymeric fixers

ABSTRACT

A cationic polymeric fixer material comprising cationic polymers and at least one marker composition soluble in the fixer material and detectable under either ultraviolet or near IR light; as well as a method of inkjet printing using said fixer material and a method of detecting cationic polymeric fixer material on a printed media using said fixer material.

FIELD OF THE INVENTION

The present invention relates to fixer materials which can be used in cationic polymeric fixers in inkjet printing and which contain a marker which makes the fixer detectable when the fixer is printed on a media surface.

BACKGROUND OF THE INVENTION

Dye-based ink-jet inks have become a dominant technology in the ink-jet ink arena. However, as many dyes are water-soluble, images printed using many of such dye-based ink jet inks are not as waterfast as may be desirable. The waterfastness and durability of an anionic dye-based ink-jet ink printed on media has been shown to be enhanced by overprinting or underprinting the printed image with a fixer, preferably from a separate pen. Fixers have been used to crash out anionic dye molecules by changing the pH of the printed inkjet image or by adding salts such as Ca²⁺ and Mg²⁺ to the printed inkjet image to crash the coloratns, e.g. anionic pigments or carboxylated dyes. These fixers had the disadvantages of lacking durability, of causing pen wear and tear and corrosion due to the high salt content and the low pH.

More recently, cationic polymers have been used in the fixer. Thus, when the cationic polymer and the anionic dye contact one another on a substrate, a reaction between the dye and the polymer creates an image with improved durability and waterfastness. Inkjet images with improved waterfastness and durability can therefore be obtained by underprinting or overprinting a printed inkjet image with a cationic polymeric fixer.

Fixer solutions are often transparent and thus invisible when printed on a medium substrate. This has necessitated the inclusion of markers or indicators so that nozzle health, pen alignment and dot placement of the fixer can be evaluated. With only weakly cationic fixers, traditional UV and near-IR indicators like Stilbene and Tinolux BBS have been used. These are anionic, sulfonated markers visualized with UV and near IR light. Such anionic indicators react with cationic polymers and thus cannot be used in a cationic polymeric fixer.

SUMMARY OF THE INVENTION

The present invention relates to a method of detecting a cationic polymeric fixer material present on an inkjet printed media, comprising

-   -   a) inkjet printing the cationic polymeric fixer material onto a         media substrate;     -   b) exposing the printed media substrate with ultraviolet or near         IR light;         wherein said fixer material comprises cationic polymers and at         least one marker composition soluble in the fixer material and         detectable under either ultraviolet or near IR light.

Furthermore, the present invention relates to a cationic polymeric fixer material comprising cationic polymers and at least one marker composition soluble in the fixer material and detectable under either ultraviolet or near IR light.

Additionally, the present invention relates to a method of inkjet printing on a media substrate, comprising:

-   -   a) inkjet printing an ink comprising an anionic colorant onto         the media. substrate;     -   b) either underprinting before step a) or overprinting after         step a) a cationic polymeric fixer material onto the media         substrate;         wherein said cationic polymeric fixer material comprises         cationic polymers and at least one marker composition soluble in         the fixer material and detectable under either ultraviolet or         near IR light.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 graphs wavelength (nanometers)(nm) vs. response (amplitude/wave)(A/W) to show the typical spectral sensitivity of silicon detectors.

FIG. 2 graphs wavelength (nm) vs. relative intensity to show the absorption and emission spectra of 4,4′-Diaminostilbene dihydrochloride.

FIG. 3 graphs wavelength (nm) vs. relative intensity to show the absorption and emission spectra of 1,1′,3,3,3′,3′-Hexamethylindodicarbocyanine iodide in water.

FIG. 4 graphs wavelength (nm) vs. relative intensity to show the absorption and calculated emission spectra of 1,1′,3,3,3′,3′-Hexamethylindotricarbocyanine Iodide in water.

FIG. 5 graphs wavelength (nm) vs. relative intensity to show the absorption spectra of Basic Violet 16 (BV16).

FIG. 6 graphs wavelength (nm) vs. percent reflectance (% R) to show the reflectance spectra of various fixer+indicators on Hammermil Fore DP (HM).

FIG. 7 graphs wavelength (nm) vs. percent reflectance (% R) to show the reflectance spectra of various fixer+indicators on Lustro Laser (LL).

FIG. 8 graphs wavelength (nm) vs. percent reflectance (% R) to show the reflectance spectra of various fixer+indicators on Fortune Matte (FM).

FIG. 9 shows comparative photographs of HM, LL, FM media printed with fixer+indicator (+0.1% DAMC) under normal office light and under UV (366 nm) light.

DETAILED DESCRIPTION

Inkjet inks with anionic colorants have been found to work well with fixer solutions comprising cationic polymers. The use of such cationic polymer fixer solutions increase durability and waterfastness of anionic colorant ink-printed images.

The fixer solution can be applied on the media substrate before, after, or both before and after the ink is printed. In a preferred embodiment, the fixer solution is applied before the ink is printed.

The fixer solution can be applied onto the media substrate by any means available to spread the fixer accurately onto the substrate surface to be printed. In a preferred embodiment, the fixer solution is filled in a thermal inkjet pen and the fixer is applied on the media before and/or after the color inks are applied. As a non-limiting example, an HP Business Inkjet 2200 can be used.

Cationic polymer fixer solutions are usually colorless and therefore invisible. As a result, a marker or indicator is desirable to be included in the fixer solution so that the nozzle health, pen alignment and dot placement of the fixer can be evaluated.

Overall, the criteria used in searching for fixer markers are as follows:

-   -   1) Cationic and non-ionic materials are preferred. Certain         zwitterionic materials may be useful. The main concern is         achieving long-term compatibility with fixer polymer.     -   2) Little absorption in the visible light region Is desirable,         so that the fixer printed area won't be seen under normal light         conditions.     -   3) High solubility in water and the fixer vehicle is important         to achieve pen reliability.     -   4) Sharp absorbance in the UV or IR region is desirable.         Fluorescence in the visible region Is also preferred, although         it is not required.     -   5) High extinction coefficient is helpful so that little         material is needed in the fixer for visualization.

Both visible dye and UV/near-IR dyes have been considered as markers for these fixer solutions. The visible dye provides the convenience of providing a way to examine the nozzle health visibly. The need to find an indicator that does not interfere with the hue of the inks is obvious. In contrast, the UV or near-IR dye interfere less with the hue of the colored inks under which it is underprinted.

There are advantages and disadvantages in both UV and near IR as well. With UV, the indicator itself is clear and no color is introduced into the fixer solution. However the sensitivity of the UV detection (as shown in FIG. 1) is so low that high loading of the UV indicator is necessary. This in turn can cause reliability problems, such as decap. In contrast, the sensitivity of the near-IR region is high, therefore less loading of the indicator is required. Furthermore, when solid state optical detectors are used, it has been found that near-IR dye indicators are more detectable than UV dye indicators.

Since most currently used UV and near-IR indicators, such as Stilbene and Tinolux BBS, are sulfonated, they are therefore anionic. The present applicants have encountered definite instability and incompatibility of the fixers when they have used such anionic indicators with cationic polymers. The overall effect is that the anionic indicators crash out over time with the cationic polymers and cause reliability issues.

The present applicants have instead found that if the UV and/or near-IR indicators are either cationic, zwitterionic or not ionically charged, they do not have the instability and incompatibility problems of conventional anionic indicators when used in a cationic polymeric fixer. A non-limiting list of examples of such indicators that are not anionic and show some detectable change under either ultraviolet or near IR light include 1,1′,3,3,3′,3′-Hexamethylindodicarbocyanine iodide (dicarbocyanine); 1,1′,3,3,3′,3′-Hexamethylindotricarbocyanine iodide (tricarbocyanine); Basic Violet 16; 4,4′-Diaminostilbene dihydrochloride (aminostilbene); Victoria Blue BO; 4-amino-benzoic acid (PABA); 7-amino-4-methyl coumarin (AMC); 7-diethylamino-4-methyl coumarin (DAMC); 3-[2-(diethylamino)ethyl]-7-hydroxy-4-methylcoumarin hydrochloride; and Carbostyril 124.

To be most effective to increase durability and waterfastness of the printed image on the medium, the cationic polymers used in the fixer need to be highly reactive to fix the anionic colorants in the printed image. In a preferred embodiment, polyguanidines and polyethyleneimines have been found to be effective cationic polymers for this purpose.

In a more preferred embodiment, the cationic polymers are polymonoguanidines, preferably poly (C₃₋₁₈-hydrocarbyl monoguanidines).

In a most preferred embodiment, the poly(C₃₋₈-hydrocarbyl monoguanidines) comprise groups selected from the group consisting of Formula (1) and Formula (2) or salts thereof:.

wherein:

-   -   each m is independently 0 or 1;     -   each Y is independently a C₂₋₁₈-hydrocarbyl group;     -   A and B are hydrocarbyl groups which together comprise a total         of 3 to 18carbon atoms; and     -   each R is independently hydrogen, alkyl, alkoxy, substituted         alkyl or substituted alkoxy.

In another most preferred embodiment, the poly(C₃₋₁₈-hydrocarbyl monoguanidines) comprise at least one group of Formula (3) or salts thereof:

wherein:

-   -   n is from 2 to 50.

EXAMPLES Example 1

Stilbene is one of the high fluorescence yielding UV dyes that has been widely used as a dye. Stilbene itself is not soluble in the fixer vehicle that is mostly water. To increase its solubility in water, charged groups such as —SO₃ ²⁻ or —NH₃ ⁺ must be attached to the stilbene. One of these stilbene derivatives, 4,4′-Diaminostilbene dihydrochloride is shown below:

The absorption and emission (excited @ 344nm) spectra of 4,4′-Diaminostilbene dihydrochloride is shown in FIG. 2. 750 ppm of 4,4′-Diaminostilbene dihydrochloride was spiked into a fixer containing a polymonoguanadine-based cationic polymer and the nozzle pattern was observed under UV exposure.

Example 2

As a fixer indicator in the near-IR range of wavelengths, two carbocyanine dyes were tested. The carbocyanines were: 1,1′,3,3,3′,3′-Hexamethylindodicarbocyanine iodide and 1,1′,3,3,3′,3′-Hexamethylindotricarbocyanine iodide. They are shown below:

The absorption and emission (excited @ 585 nm) of dicarbocyanine is shown in FIG. 3.

In the case of tricarbocyanine, there is one more ethylene group on the chain. The higher conjugation shifts both the absorption and emission further to the red region as shown in FIG. 4. Since the measuring limit is only up to 850 nm, the emission curve on the FIG. 4 is a calculated curve based on the dicarbocyanine data where the distance of λ_(max) for absorption and emission is 60 nm. From the absorption and emission standpoint, the tricarbocyanine would be a better choice due to a clearer fixer solution and higher detection sensitivity. Unfortunately, introduction of the ethylene group to the chain decreases the tricarbocyanine solubility in water. 750 ppm of tricarbocyanine was not soluble in the polymonoguanadine thermal inkjet fixer.

Based on this experiment, dicarbocyanine was good enough to use as a marker in the cationic polymer fixer. Tricarbocyanine would work better if there was higher detection sensitivity since the dye has only limited solubility.

Example 3

As indicated above, visible indicators would, be easiest to use since any thermal inkjet grade cationic dyes, such as Basic Violet 16, can be used. Although thermal inkjet grade quality Basic Violet 16 was not available, the grade used worked fine in the test. In order to see the nozzle pattern, it was found that the loading must be a least 750 ppm. FIG. 5 shows the absorption spectra of Basic Violet 16 in water.

Example 4

Fixer solutions were made by mixing a water based fixer containing a polymonoguanadine cationic polymer with an IR or UV absorber indicator. The list of indicators and some of their characteristics are summarized in the Table below. It was found that some of the indicators did not satisfy all of the criteria that would be desirable as indicated above. Most of the indicators that were not soluble in polymonoguanidine fixer or show strong color were eliminated from printing experiments (as indicated under “Print Evaluation”). Three media were printed with various fixers+indicators on a modified HP2200 printer: Hammermil Fore DP (HM), Lustro Laser (LL) and Fortune Matte (FM). In general, Fixer+indicator was difficult to detect on HM and FM and possible to detect on LL but not easy to achieve under UV illuminant.

The % R of fixer+indicator printed area as well as the media itself was measured with a Cary Spectrometer using diffuse mode. The spectra on HM, LL and FM printed with various fixers are shown in FIGS. 6-8 respectively.

Hammermill Fore DP

All indicator-containing fixers showed similar results to the fixer itself without indicator when the print is illuminated under UV (366 nm) except for 0.1% DAMC. The contrast between the fixer+indicator printed area and the media was visible but very poor. The reflectance measurements showed that with 0.1% PABA and 1ppm Tinosorb FR there was a slight decrease in reflectance at 260 nm or so. With 0.1% DAMC, the fixer+indicator printed area was brighter than the media and was most visible under UV among all the indicators tested (shown in FIG. 9).

Lustro Laser

The contrast between the fixer+indicator printed area and the media was visible with the fixer+indicator printed area appearing darker under UV illumination. Not much difference was seen among different additives under UV except for AMC, DAMC and Carbostyril 124. With AMC, DAMC and Carbostyril 124, fixer printed area is brighter than the media.

Fortune Matte

The fixer+indicator printed area is brighter than the media under UV, contrary to what is observed on HM and LL. The contrast is actually quite good when viewed under UV. At ˜260 nm the reflectance measurements for media and fixer+indicator printed area are almost identical except that PABA (4-aminobenzoic acid} shows slightly high reflectance than the media alone. Again, the 0.1% DAMC works well under UV.

Overall, there Is a slight difference seen in the UV region with PABA @260 nm, which may not be sufficient enough for detection. Fixer with 0.1% DAMC works the best of all the materials screened on HM, LL and FM under UV illumination. It also shows a small peak of reflectance around 210-230 nm on all three media tested. TABLE Solubil- Solubil- Print Evaluation λmax Fluorescent ity @ ity @ (view under UV Compound Charge (nm) under UV? 0.1% 0.01% Color @ 366 nm) 2-[4-(Dimethylamino) + 369 No No Not Orange XXXXXXXXXXXX styryl]pyridine tested 4-Aminobenzoic acid z ? No Yes Yes Clear Similar to Control. (PABA) Some changes in % R @ ˜260 nm on HM, LL and FM. 4-Methylesculetin n 348 No No No Clear XXXXXXXXXXXX 7-Amino-4-methyl + 354 Yes No Yes Clear No fixer can be coumarin seen on HM. Fixer is visible on LL and FM. 7-Diethylamino-4- + ? Yes Yes Yes Slightly Fixer visible under methyl coumarin yellow UV on HM, LL and FM. 3-[2-(Diethylamino) + ? Yes Not Yes Slightly Fixer slightly ethyl]-7-hydroxy-4- tested yellow visible on HM. methylcoumarin Fixer visible on LL hydrochloride and FM. Carbostyril 124 + 350 Yes No Yes Clear Fixer slightly visible on HM. Fixer visible on LL and FM. Cationic copper + 768 No No No Blue- XXXXXXXXXXXX phthalocyanine Green Coumarin 152 n 395 Yes No No Slightly XXXXXXXXXXXX Yellow Coumarin 7 + 438 Yes No No Yellow XXXXXXXXXXXX Direct Yellow 9 − 402 No No Not Yellow XXXXXXXXXXXX Tested FluorescentBrightner28 z 350 Yes No No Clear XXXXXXXXXXXX Indocyanine Green − 775 No No No Green XXXXXXXXXXXX IR140 + 823 No No No Pale Blue XXXXXXXXXXXX Lumichrome + 392 Yes No No Clear XXXXXXXXXXXX Pinacryptol Yellow + 385 No No Not Yellow XXXXXXXXXXXX tested Thioflavin T + 412 No No Yes Yellow XXXXXXXXXXXX Tinosorb FR z ? Yes No No Clear Similar to control Dispersion (clear at 0.001%) Variamine Blue + 377 No Yes Yes Yellow XXXXXXXXXXXX Victoria Blue BO + 619 No Not Yes Blue Visible under IR (Fluorescent tested under IR) Control (Fixer only) Fixer barely visible on HM, slightly visible on LL, visible on FM. Note: 1) The “charge” indicated is a rough estimate of the charge of the compound in the fixer solution based on the chemical structure of the compound. No detailed study of pKa was done. “+” indicates positively charged materials, “−” indicates negatively charged materials, “n” indicates nonionic materials and “z” indicates zwitterionic materials which carry a net zero charge. 2) The solubility is based on the solubility of the compound in a 4 wt % polymonoguanadine fixer. 3) “Color” refers to the color of the fixer solution in the presence of the compound. 4) The X'ed blocks indicate insufficient solubility and/or strong color present. These chemicals are not suitable for fixer indicator.

Other embodiments of the invention will be apparent to those skilled in the art from a consideration of the specification or practice of the invention disclosed herein. It is intended that the specification and examples be considered as exemplary only, with the true scope and spirit of the invention being indicated by the following claims. 

1-7. (canceled)
 8. A cationic polymeric fixer material comprising cationic polymers and at least one marker composition soluble in the fixer material and detectable under either ultraviolet or near IR light.
 9. The cationic polymeric fixer material of claim 8 wherein the marker composition is selected from the group consisting of 1,1′,3,3,3′,3′-Hexamethylindodicarbocyanine iodide (dicarbocyanine); 1,1′,3,3,3′3′-Hexamethylindotricarbocyanine iodide (tricarbocyanine); Basic Violet 16; 4-amino-benzoic acid (PABA); 4,4′-Diaminostilbene dihydrochloride (diaminostilbene); Victoria Blue BO; 7-amino-4-methyl coumarin; 7-diethylamino-4-methyl coumarin (DAMC); 3-[2-(diethylamino)ethyl]-7-hydroxy-4-methylcoumarin hydrochloride; and Carbostyril
 124. 10. The cationic polymeric fixer material of claim 8 wherein the cationic polymers are selected from the group consisting of polyguanadines and polyethyleneimines.
 11. The cationic polymeric fixer material of claim 10 wherein the cationic polymers comprise polymonoguanadines.
 12. The cationic polymeric fixer material of claim 11 wherein the polymonoguanadines are poly (C3-18-hydrocarbyl monoguanidines).
 13. The cationic polymeric fixer material of claim 12 wherein the poly(C3-18-hydrocarbyl monoguanidine) comprises groups selected from the group consisting of Formula (1) and Formula (2) or salts thereof:

wherein: each m is independently 0 or 1; each Y is independently a C2-18-hydrocarbyl group; A and B are hydrocarbyl groups which together comprise a total of 3 to 18 carbon atoms; and each R is independently hydrogen, alkyl, alkoxy, substituted alkyl or substituted alkoxy.
 14. The cationic polymeric fixer material of claim 12 wherein the poly(C3-18-hydrocarbyl monoguanidine) comprises at least one group of Formula (3) or salts thereof:

wherein: n is from 2 to
 50. 15. A method of inkjet printing on a media substrate, comprising: a) inkjet printing an ink comprising an anionic colorant onto the media substrate; b) either underprinting before step a) or overprinting after step a) a cationic polymeric fixer material onto the media substrate; wherein said cationic polymeric fixer material comprises cationic polymers and at least one marker composition soluble in the fixer material and detectable under either ultraviolet or near IR light.
 16. The method of claim 15 wherein the at least one marker composition is selected from the group consisting of 1,1′,3,3,3′,3′-Hexamethylindodicarbocyanine iodide (dicarbocyanine); 1,1′,3,3,3′3′-Hexamethylindotricarbocyanine iodide (tricarbocyanine); Basic Violet 16; aminostilbene4-amino-benzoic acid (PABA); 4,4′-Diaminostilbene dihydrochloride (diaminostilbene); 7-amino-4-methyl coumarin (AMC); 7-diethylamino-4-methyl coumarin (DAMC); and Carbostyril
 124. 17. The method of claim 15 wherein the cationic polymers are selected from the group consisting of polyguanadines and polyethyleneimines.
 18. The method of claim 17 wherein the cationic polymers comprise polymonoguanadines.
 19. The method of claim 18 wherein the polymonoguanadines are poly (C3-18-hydrocarbyl monoguanidines).
 20. The method of claim 19 wherein the poly(C3-18-hydrocarbyl monoguanidine) comprises groups selected from the group consisting of Formula (1) and Formula (2) or salts thereof:

wherein: each m is independently 0 or 1; each Y is independently a C2-18-hydrocarbyl group; A and B are hydrocarbyl groups which together comprise a total of 3 to 18 carbon atoms; and each R is independently hydrogen, alkyl, alkoxy, substituted alkyl or substituted alkoxy.
 21. The method of claim 19 wherein the poly(C3-18-hydrocarbyl monoguanidine) comprises at least one group of Formula (3) or salts thereof: 